We report a molecular dynamics study of the solvation of the UO22+ and Eu3+ cations and their chloro complexes in the [BMI][PF6][H2O] "humid" room-temperature ionic liquid (IL) composed of 1-butyl-3-methylimidazolium(+) and PF6- ions and H2O in a 1:11 ratio. When compared to the results obtained in dry [BMI][PF6], the present results reveal the importance of water. The "naked" cations form UO2(H2O)(5)(2+) and Eu(H2O)(9)(3+) complexes, embedded in a shell of 7 and 8 PF6- anions, respectively. All studied UO2Cln2-n and EuCln3-n chloro complexes remain stable during the dynamics and coordinate additional H2O molecules in their first shell. UO2Cl42- and EuCl63- are surrounded by an "unsaturated" water shell, followed by a shell of BMI+ cations. According to an energy component analysis, the UO2Cl42- and EUCl63- species, intrinsically unstable toward dissociation, are more stable than their less halogenated analogues in the IL solution, due to the solvation forces. The different chloro species also interact better with the humid than with the dry IL, which hints at the importance of solvent humidity to improve their solubility. Humidity markedly modifies the local ion environment, with major consequences as far as their spectroscopic properties are concerned. We finally compare the aqueous interface of [BMI][PF6] and [OMI][PF6] ionic liquids, demonstrating the importance of imidazolium substituents (N-butyl versus N-octyl) to the nature of the interface and miscibility with water.